Process for preparing chloro-fluoro methane from phosgene and hydrogen fluoride



United States Patent O 'PROCESS FOR PREPARING CCHLORQ-FLUORO METHANE FROM PHOYSGENE AND HYDRO- GEN FLUORIDE Donald D. Coffman, West Chester, Pa.,-.and Charles W. Tullock, Wilmington, Del., assiguors to E. I. du Pont `de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 18, 1955,

Serial No. 489,296

s claims. (ciano-653) This invention relates to a new" process of preparing ilumine-containing organic compounds. larly, it relates to a process of preparing completely halogenated methanes in whichat least one of the halogen atoms is iluorine, any other halogen being chlorine. These compounds, which include carbon tetrauoride and the chlorolluoromethanes, will be referred to hereinafter as duerme-containing perhalomethanes.

The ilumine-containing perhalomethanes are extremely valuable compounds, finding extensive use as refrigerant liquids,` as dielectric fluids and as ingredients of insecticidal compositions, e. g., as propellants in aerosols. Carbon tetrailuoride is the starting material ina new process (disclosed in Serial No. 390,441, now abandoned, vfiled by M. W. Farlow `on November 6, 1953, a continuationin-pa'rt-'of which has been issued as U. Si Patent 2,709,192)

"ot synthesizing the industrially important tetrauoroethylene, wherein carbon teralluoride is reacted with carb'onv at very' high temperatures, e. g., in a carbon arc.

This invention has as an object the provision of a process forthe preparation of'perhalomethanes containingy luorine. A further object is the provision of a process for preparingy compounds of the formula CFeCls-e wherein F is an' integer from 1 to 4. Other objects will: appear hereinafter.

These objects are accomplished by the present invention of a process for preparl'ngthe ilumine-containing perhalUme'thaneS, i. e., carbon tetrafluoride andthe chloro- .iluorornethanea which comprises vreacting hydrogen fluoride with carbon and phosgene, the latter being used as the preformedrphosgene or Inade in situ from its components, carbon 'monoxide and-chlorine, ata temperature Within the rangeiof about 600 C. to about 1500" C., and

' isolating the ilumine-containing perhalornethanes formed.

TheV phosgene employed in the reaction can be preformedor it can beformed'in situ from. carbon monoxide andl chlorine which. are known to combine readily at elevated temperature to 'give phosgene.

necessarily, usedin `excess over the amount calculated to^react with the-chlorine. Thehydrogen fluoride is used in' substantially anhydrous form. Commercial hydrogen fluoride is satisfactoryfor this purpose. The carbon can beiused` in any form, including` coal, graphite, charcoal, the' various fo'rmsofy carbon black such asv lamp black, acetylene black, bone black, etc. In general, higher conversions are obtained with active carbon, and preferably activel charcoal,` of .vvhich'many varieties are obtainable con'lmercially; Active carbon'` is very linely divided, porous' carbon having a total surface area of at least 20 square meters per` gram (Hassler, Active Carbon, Chemical Publishing Co., 1951, p. 127). The carbon need' not be rigorously pure and it may, for example, containthe normal amount of ash, e. g., from 0.5 to 4% `by weight inthe case offmost active carbons. However, it should` be substantially anhydrous. dehydratethe carbon prior to reaction since carbon, espe- More particul When this is done, the carbon monoxide is preferably, though not It is desirable to,

V2 ci'ally 4of the active k'or absorbent variety, can retain signiiicant amounts of water' even atf high temperatures.

As promoter for lthe reaction there 'can be employed a catalytic amount, e. g., from '0 5 Ato5 moles, per 100 moles of hydrogen tluoride, of a halide of a metal Vin which halide the metal is inA a vala-nce stage of" 3' to 5 and the halogen is a normally gaseous halogen, i.v e., fluorine or chlorine, including antirnonyE pelitfachlo'ride, aluminum triuoride, tin tetrachloride, ferrie fluoride, ferrie chloride, ete. Where the metal halide is Vvelatileit` can be introduced with the gaseous reactants. Where it-i'sA substantially non-volatile at the reaction' temperature-it can be admixed With the carbon.

Whfiie' the relative ratios of 'the reactants are not critical,'it`is desirable, in order-to direc'tthe reaction toward the formation ofT the` more desirablec'a-rbon tetrafluonide, that the reaction' mixture contain 'at least one' mole of hydrogen lluorid'e` per mole of phosgen'e.` The best re- .stilts.are.obtained'whenl the molar ratioof hydrogen lluori'detophosgenenis between about 1":l and' 3'5 l. The carbonis normally usedz in excess 'of the 'othery reactants.

At temperatures below' annui 600 @xt-here is obtained only avery small amount of the perhalomethanes, the main 'reaction' product'being carbonyl llu'oride, as disclosedin-v applicationfSeriall No; 489,294, filed'fby'C. .V. Tullock of'even dateherewith. v Itis therefore notpractical to operate below about 600 C. Attemperatui'es'foff about 1500 C. and above -o'ther products, including tetrafluoroethylene, begin to be formed in significant amounts. Thus, to obtain :practical yields of carbon tetra'uo'ride and the` chlorolluoronlethanes, itis desirable to work within the" range of about '600 C. torabou't 15010"n C. The preferred 'temperature range is that hetween 700"I C. and 1`200 yC.

The reaction-can be carried1 out in 'sealed pressurevessels at' the autogeneo'u's' pressure developed by' the reactents and reaction products at `the operating temperature. However, Ait isV much" more conveniently carriedfout at or near atmospheric pressure, 1e. g., at pressures between about 50 mm. of mercury and?. or 3 atmospheres, in a tubular reactor'pa'cked with carbon. `lin this I,type of operation, a gaseous mixtureiinthe proper proportions of hydrogen fluoride and phosgene, or of hyd'ro'geuiiuoride, 'carbon monoxide and chlorine is passed through thereactor heated tothe 'desired' temperature.. It isl some'tirl'ies desirable to operate at pressures slightly lessyth'an atmospheric so as to obviat'e any leak from' 'the apparatus. The contact time is not very criticalsirlce appreciable conversions are observed even at short contact tinl'es,`e'. g.,`two seconds; Good results are obtainediiat contacttinles in the range of 5980seconds,,although-much longer'eentac't timesean be used, e. g., 10 minutes ormor'e.

Because of the'pre'senee inA the reaction mixture of hydrogen' fluoride andy chlorine, there are only'fevv suitable materials of construction forthereaeton since almost all materials are-rapidly attacked by one ortheotherof these corrosive gases at'tlrehigh temperaturesrequired. At-jor hearthe lower end of theternperature range, nickel" tubes or platinumlinedtubes 'can'.be usedbn't they'fail'at'hlghe'r temperatures. The most suitable reactors are"'g`raphite tubes. Alumina tubes made of high purity alumina are also satisfactory if the temperaturedoes notexceed about 1.00ctl C. l i i The reaction product contains, besides` Carbon tetrafiuoride andthe chlorolluoromethanes, .substantial amounts of'` carbonyl fluoride and carbonyl chloroiluoride. In addi= tion, it contains the hydrogen chloride formed in the reaction, unreacted phosgene and generally chlorine,` the latter being. either introduced as afreactant or formed from the phosgene used. Carbon dioxide and carbon monoxide are also present. ,If it is desired to' isolate only the ilumine-containing pelhlo'methane's, vthe most Cohvenient procedure consists in treating the eluent gas with water or an alkaline solution, e. g., aqueous sodium hydroxide, to remove all acidic or hydrolyzable products (hydrogen chloride, hydrogen lluoride, chlorine, carbonyl fluoride, carbonyl chlorouoride, carbon dioxide and phosgene), after which the alkali-insoluble product is fractionally distilled to separate the components. If it is desired to recover also the carbonyl fluoride and carbonyl chloroiluoride present, the reaction mixture should be treated to remove the hydrogen chloride, since the latter has the same boiling point as carbonyl fluoride and is not separable therefrom by fractionation. This is done according to the process described and claimed in the concurrently led Tullock application Serial No. 489,294. Briefly stated, this Iprocess consists in treating the reaction mixture with an agent (alkali metal fluoride, sulfur trioxide or phosphorus pentoxide) which absorbs the hydrogen chloride without affecting the carbonyl fluoride. The reaction mixture, with or without a preliminary separation therefrom, by cooling to an appropriate temperature, of unreacted phosgene and/ or hydrogen fluoride, is brought into contact with at least a stoichiometric amount, based on the hydrogen chloride in the reaction product and on any hydrogen fluoride there present, of the absorbing material, and contact is maintained at a temperature at least as high as C. until substantially all of the hydrogen chloride is removed. The remaining product is then fractionally distilled to separate the various constituents.

The invention is illustrated in greater detail in the following examples.

Example I The reactor was a graphite tube 28.5" long, 1" outside diameter and 0.75 inside diameter, placed inside a nickel tube. The center portion of the graphite tube was packed with 65 ml. of activated charcoal, which filled 9 inches of the tube. The heated portion of the tube (13 inches) comprised this center portion. Prior to reaction, the activated charcoal was dehydrated by heating it at 800 C. for 14-16 hours in a slow stream of helium.

The reactants (phosgene and hydrogen fluoride in this example) were weighed separately, then combined in a stainless steel cylinder, which was then warmed to 42-47 C. and from which the reactant mixture was bled at a predetermined rate. A slow stream of helium was used as the carrier gas.

At the exit end of the reactor tube was a train of receivers consisting of two copper traps cooled in a carbon dioxide/ acetone mixture, followed by two glass traps cooled in liquid nitrogen. The system was protected from atmospheric moisture.

A mixture of 46.5 g. (0.47 mole) of phosgene and 20.6 g. (1.03 moles) of commercial anhydrous hydrogen fluoride was placed in the feed cylinder. Of this mixture, a total of 56.5 g. was passed through the reactor tube heated at 775-850 C. over a period of 3.8 hours. The product collected in the carbon dioxide/ acetone traps during the entire run amounted to 5.5 g. This material Was bled into a stainless steel cylinder containing 80 g. of anhydrous sodium lluoride. After remaining in contact with this absorbent for 24 hours at room temperature, all the hydrogen fluoride and hydrogen chloride present had been removed. The residual product, which amounted only to 1.5 g., was not analyzed.

A first portion (38%) of the reactant mixture was passed through the tube at the rate of 0.72 g. per minute.

From this first portion there was received in the liquid nitrogen traps l1 g.V of condensate. This material was bled into a cylinder containing 80 g. of sodium fluoride and Lcooled in liquid nitrogen. Any carbon monoxide present was removed by pumping off the cylinder down to a pressure of 0.2 mm. of mercury, after which the cylinder was sealed and allowed to stand at room temperature for 24 hours. The residual product, which was thus freed of carbon monoxide, hydrogen fluoride and hydrogen chloride, weighed 4.0 g. Infrared analysis showed that it contained, on a molar basis, 10% GF4, 25% GFsCl, 25% COFz, 2% COFGI, 15% CO2 and 1% or less each of GFzGlz, COGlz, and SiF4 (the latter through hydrolysis by adventitious water and reaction of the hydrogen fluoride formed with the glass of the analytical cell). Chlorine was also present.

The remainder of the reactant mixture was passed through the tube at the following rates: 30% at 0.20 g./min,. 20% at 0.26 g./min., and 12% at 0.10 g./min. The total condensate in the liquid nitrogen traps from this second portion amounted to 27.5 g. It was treated for removal of CO, HF and HC1 as described above, after which treatment it weighed 13.0 g. This material was found by infrared analysis to contain, in moles per cent, 25% GF4, 15% GFaCl, 35% COF2, 5% CO2, 1% each of GFzClz, COClz, and SiF4. Chlorine was also present.

From these data it can be calculated that the conversion of hydrogen uoride to carbon tetrafluoride in this entire run was about 20%.

Example Il In a run similar to that described in Example I, 35.5 g. of a reactant mixture made up of 0.77 mole of hydrogen fluoride and 0.34 mole of phosgene was passed, at the rate of 0.455 g. per minute, through a graphite-lined reactor tube partly packed with active charcoal and heated at 800 C. In this case, a serious leak developed in the apparatus because the reactor tube was provided with a nickel thermocouple well which was deeply corroded by the chlorine formed at the reaction temperature. This was shown by the fact that only 15 g. of the 35.5 g. input was recovered, and that 8.5 g. of yellow nickel chloride was removed from the tube at the end of the reaction. The product collected in the carbon dioxide/ acetone traps (4.5 g.) was all unchanged hydrogen fluoride. The product collected in the liquid nitrogen traps (10.5 g.) was freed from carbon monoxide and hydrogen chloride as described in Example I. There was left 2.0 g. of a material which infrared analysis showed to contain, on a molar basis, 45% carbon tetrailuoride, 25 chlorotriiluoromethane, 20% carbon dioxide and 0.5% dichlorodilluoromethane.

Example III Using the apparatus and procedure described in Example I, except that the active charcoal was replaced by a commercial acetylene black (Shawinigan black), a mixture of 44.6 g. (0.45 mole) of phosgene and 20 g. (1.0 mole) of hydrogen fluoride was passed through the reactor at 775-850 C. during a period of 2.8 hours. A portion (49%) of the reactant mixture was put through at the rate of 0.51 g./minute, another portion (31%) at the rate of 0.33 g./rninute and the remainder at the rate of 0.23 g./minute. The total product condensed in the liquid nitrogen traps amounted to 24.0 g. After treatment to remove CO, HF and HCl as described in Example I, there was left 12.5 g. of product which infrared analysis showed to contain, in moles per cent, 5% GF4, 20% CFsCl, 15% G0132, 3% COFCl, 7% CO2, 1% each GOClz and SiF4, and a small amount of GF2G12. Chlorine was also present. The material condensed in the carbon dioxide/ acetone traps contained small amounts of GF4 and CFaGl.

Example IV graphite reactor tube was packed with 65 ml. of active charcoal and heated to 775-850 C. There was passed through the tube during a period of 4.5 hours a reactant mixture of 39 g. (0.55 mole) of chlorine and 19.5 g. (0.98 mole) of hydrogen fluoride, together with excess carbon monoxide. Twenty-nine per cent of the reacant mixture was passed through at the rate of 0.28 g./ minute and the rest at the rate of 0.14 g./minute. The total condensate collected in the liquid nitrogen traps amounted to 45.0 g. lt was treated as described above to remove CO, HF, and HC1, after which there was left 17.0 g. of product, which infrared analysis showed to contain, on a molar basis, 25 GF4, 25% CFaCl, 35% COF2, 10% CO2, 5% COFCl, 1% CFzClz and traces of COClz and SiFl. The material condensed in the carbon dioxide/ acetone traps was mostly hydrogen fluoride and phosgene, with a small amount of dichlorouoromethane. The conversion of hydrogen fluoride to carbon tetrauoride was about 21%.

The ilumine-containing perhalomethanes produced according to the process of this invention can be separated from the other components by fractionation at low ternperature and elevated pressure. For example, a suitable fractionating sill comprises a monel metal column 45" high and 1.75 internal diameter packed with small stainless steel rings. The still is designed, like all low temperature/ elevated pressure stills, to distill at Substantially constant temperature. Cuts are made as the pressure changes. The still head is surrounded by coils through which acetone cooled in a carbon dioxide/acetone bath is circulated. As already noted, fractionation will not separate hydrogen chloride from carbonyl fluoride. if it is desired to recover the-latter in a substantially pure state, the hydrogen chloride should rst be removed from the reaction product as described above. However, carbon tetrafluoride can readily be separated by fractionation with or without prior removal of the hydrogen chloride. If only carbon tetralluoride and the chlorouoromethanes are desired, it is convenient to remove first all the acidic and hydrolyzable components from the reaction product,

then fractionate the remainder at low temperature and elevated pressure.

The foregoing detailed description has been given for clear-ness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described for obvious modifications will occur to those skilled in the art.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Process for the preparation of perhalomethanes of the formula CFCLrwherein x is an integer from 1 to 4 which comprises bringing hydrogen fluoride and phosgene in contact with carbon under essentially anhydrous conditions at a emperature within the range from about 600 C. to about 1500 C.

2. Process according to claim 1 wherein 'the reaction is conducted in a continuous ow system at about atmospheric pressure.

3. Process for the preparation of perhalomethanes of the formula CFIClfrwherein x is an integer from 1 to 4 which comprises bringing hydrogen fluoride and phosgene in contact with carbon under essentially anhydrous conditions at a temperature within the range from about 700 C. to about 1200 C.

4. Process for the preparation of carbon tetrailuoride which comprises bringing hydrogen fluoride and phosgene in contact with carbon under essentially anhydrous conditions at a temperature within the range from about 600 C. to about 1500 C. and isolating the carbon tetrailuoride.

5. Process for the preparation of carbon tetrafluoride which comprises bringing hydrogen fluoride and phosgene in contact with carbon in a continuous flow system, at about atmospheric pressure, under essentially anhydrous conditions, and at a temperature within the range from about 700 C. to about 1200" C. and isolating the carbon tetrafluoride.

No references cited. 

1. PROCESS FOR THE PREPARATION OF PERHALOMETHANES OF THE FORMULA CFXCL4-X WHEREIN X IS AN INTEGER FROM 1 TO 4 WHICH COMPRISES BRINGING HYDROGEN FLUORIDE AND PHOSGENE IN CONTACT WITH CARBON UNDER ESSENTIALLY ANHYDROUS CONDITIONS AT A TEMPERATURE WITHIN THE RANGE FROM ABOUT 600* C. TO ABOUT 1500* C. 